- The unusual reactivity of C F OCF CF with PBu and the complex hydrides M[EH] (M: Li, Na; E: B, Al); preparation of potassium perfluoro-2-propoxyeth-1-enyltrifluoroborate K[C F OCF CFBF]
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The nucleophilic hydrodefluorination of C3F7 OCF=CF2 with the complex hydrides Li[AlH4], Li[BH4] or Na[BH4] proceeded non-stereoselectively and was accompanied by the formation of either cis- and trans-C3F7OCH=CFH and/or C3F7 OCHFCF2H. The reaction of C3F7 OCF=CF2 with PBu3 followed by treatment with BF3·OMe2 or BF3· OEt2 yielded [C3F7OCF=CFPBu3] [BF4] (cis and trans) and, probably, [trans -Bu3 PCF=CFPBu3] [BF4]2. The hydrolysis of the latter with pure water proceeded quickly while the former isomeric mixture formed the isomeric olefins C3F7OCF=CFH slowly. The usage of aqueous NaOH instead of water produced mainly trans -HF=CHF. The metallation of C3F7OCF=CFH (cis:trans=45:55) to C3F7OCF=CFLi and its subsequent reaction with B(OMe)3 and K[HF2] gave the salt K[C3F7OCF=CFBF3] in a different cis to trans ratio (25:75) with satisfactory yield.
- Frohn, Hermann-Josef,Bardin, Vadim V.
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Read Online
- Application of perfluoro(2-propoxypropyl vinyl ether) (PPVE-2) in the synthesis of perfluoro(propyl vinyl ether) (PPVE-1)
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A novel preparative method for the conversion of n-C3F7OCF(CF3)CF2OCF = CF2 (PPVE-2) into n-C3F7OCF = CF2 (PPVE-1) is reported. It includes the catalytic oxidation of PPVE-2 with molecular oxygen to furnish a mixture of carbonyl fluorides which are subjected to alkaline hydrolysis resulting in a mixture of salts. Subsequent thermolysis of those salts give rise to an inseparable mixture of PPVE-1 and perfluoro-2-propoxypropanoyl fluoride. Treatment of this mixture with sodium carbonate allowed to obtain sodium perfluoro-2-propoxypropionate and to isolate PPVE-1. Thermolysis of this sodium salt produced an additional amount of PPVE-1, so that the total conversion of PPVE-2 into PPVE-1 is accomplished in good yields. The reaction conditions, the choice of reagent as well as the course of competitive reactions are discussed.
- Hintzer, Klaus,Hirschberg, Markus E.,Pajkert, Romana,R?schenthaler, Gerd-Volker,Smith, Sean M.,Tverdomed, Sergey N.
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- A fluorinated alkyl vinyl ether of preparation method
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The invention discloses a fluoroalkylvinyl ether preparation method. The method comprises the following steps: carrying out a film forming reaction on perfluoroalkyloxypropionyl fluoride by a salt forming agent under the action of an aprotic alcohol ether catalyst at 20-80DEG C, and carrying out a decarboxylation reaction at 110-150DEG C to prepare corresponding fluoroalkylvinyl ether. The preparation method has the advantages of high raw material conversion rate, simple process, no need of a solvent, and the like.
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Paragraph 0025; 0026
(2017/02/24)
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- Method for Preparing Fluorine-Containing Vinyl Ether
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Provided is a method for preparing fluorine-containing vinyl ether. The method comprises: carrying out hydrolytic neutralization on a small molecular weight byproduct which is produced in the process of preparing perfluoropolyether or a perfluorinated surfactant by photooxidation of fluorine-containing olefin; and obtaining fluorine-containing vinyl ether by drying and cracking. The byproduct produced in the process of preparing perfluoropolyether or the perfluorinated surfactant is utilized, thereby solving the emission problem of industrial wastes, reducing environment pollution, and generating available fluorine-containing vinyl ether.
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Paragraph 0030-0032
(2014/11/13)
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- COMPOUND HAVING PERFLUORO(4-METHYLENE-1,3-DIOXOLANE) STRUCTURE AND NOVEL POLYMER
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Disclosed are a compound having a perfluoro(4-methylene-1,3-dioxolane) structure which has not been known yet, and a novel polymer. Specifically disclosed are a compound represented by the formula (a) below which has a perfluoro(4-methylene-1,3-dioxolane) structure, a method for producing such a compound, a novel compound useful for producing such a compound, and a novel polymer containing a repeating unit represented by the formula (A) below. (In the formulae, RF1-RF4 independently represent a fluorine atom, a chlorine atom or a monovalent perfluorinated saturated organic group having 1-20 carbon atoms.)
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Page/Page column 20-21
(2010/02/15)
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- PROCESSES FOR PRODUCING FLUORINATED ESTER, FLUORINATED ACYL FLUORIDE, AND FLUORINATED VINYL ETHER
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A process for producing a fluorinated ester through a small number of steps, is presented. The process for producing a fluorinated ester, comprises a transesterification step in which RAF-COOCF2-RAF and RA-CH2OH are subjected to a transesterification reaction to obtain RAF-COOCH2-RA, and a fluorination step in which the obtained compound is fluorinated to obtain a reaction product containing RAF-COOCF2-RAF. Here, in the formulae, RA is a monovalent organic group, and RAF is the same group as RA or a monovalent organic group obtained by fluorination of RA.
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Page/Page column 15
(2008/06/13)
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- Polyfluorinated ethers: IV.* By-products in the synthesis of polyfluorinated alkyl vinyl ethers in a solvating solvent
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By-products formed in the synthesis of perfluoro(propyl vinyl ether), perfluoro(2-propoxypropyl vinyl ether), and methyl perfluoro(4-vinyloxybutanoate) in a solvating solvent have been studied. 1998 MAHK "Hayka/Interperiodica".
- Yuminov
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p. 1715 - 1720
(2007/10/03)
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- Radical additions to fluoro-olefins. Photochemical mono-fluoroalkylation and sequential bis-fluoroalkylation of oxolane
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Oxolane was fluoroalkylated by its photoadditions under atmospheric pressure. Monofluoro-alkylations were carried out with hexafluoropropene (1) and perfluorovinyl ethers C3F7O-[CF(CF3)CF2O]n-CF=CF2 (2-4, n=0-2) by direct photoexcitation of the oleflns to give high yields of addition products 9-12 (81-94%). The reactions were completely regioselective at the oxolane molecule and almost completely regioselective (93-99%) at the double bond of fluoro-olefins; no bis-fluoroalkylated oxolanes were detected. The completely selective introduction of a second fluoroalkyl into position 5 of the oxolane molecule was accomplished by acetone-sensitised photoaddition of 2-fluoroalkylated oxolanes 9, 10 to fluoro-olefins 1 and 2. Byproducts from reactions of the dimethylketyl radical which is formed in the initiation step were isolated and have given some evidence about the reaction mechanism that is discussed.
- Paleta, Oldrich,Cirkva, Vladimir,Kvicala, Jaroslav
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p. 125 - 134
(2007/10/03)
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- Polyfluoroalkyl Polyfluorovinyl Ethers. I. Kinetics and Mechanism of Formation of Perfluoropropyl Perfluorovinyl Ether from Sodium Perfluoro-2-methyl-2-oxahexanoate
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The kinetics and mechanism of decarboxylation of sodium perfluoro-2-methyl-3-oxahexanoate have been studied in aprotic (diethylene glycol dimethyl ether) and protic (ethylene glycol) solvents.In the synthesis of perfluoropropyl perfluorovinyl ether, the concurrent formation of 1,3,3,3-tetrafluoroethyl perfluoropropyl ether is thermodynamically more favorable.
- Yuminov, V. S.
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p. 1037 - 1039
(2007/10/03)
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- THERMOGRAPHIC INVESTIGATION OF THE DECARBOXYLATION OF SALTS OF PERFLUORINATED CARBOXYLIC ACIDS
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The thermal stability of the salts of metals of the first group with perfluorinated carboxylic acids was investigated by a differential thermal method.The calculations of the A, E, and n parameters were made on a Minsk 32 computer.For the investigated series of salts the reactions has first-order kinetics.In the case of the pyrolysis of the salts of perfluoromethoxypropionic acid the yield of perfluoromethyl vinyl ether depends not only on the cation of the salt but is determined to a significant degree by the structural features of the carbon skeleton.Tetrafluoroethylene and perfluoromethoxypropionyl fluoride were detected as side products.A mechanism for the process, which explains the formation of the main reaction products, was proposed and confirmed experimentally.
- Gubanov, V. A.,Zevakin, I. A.,Gurari, V. E.,Tumanova, A. V.,Dolgopol'skii, I. M.,et al.
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p. 1409 - 1412
(2007/10/02)
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- FLUORO-KETONES IV. SYNTHESIS OF PHENYLPERFLUOROALKYL KETONES - MECHANISM OF REACTION BETWEEN PHENYLLITHIUM AND FLUOROESTERS
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Although fluorine containing ketones (RfC(O)Rf and RfC(O)R, Rf = perfluoroalkyl) have been prepared from the reaction between organolithium reagents and perfluoroalkyl esters, the reaction has not found general applicability.Variable yields of ketones and co-production of secondary and tertiary alcohol by-products have in most instances been experienced.We have examined in more detail the factors e.g., temperature, mode of addition and perfluoroalkyl ester structure which influence ketone product and by-products formation.By controlling experimental conditions excellent yields of C6H5C(O)Rf compounds can be attained.A lithium salt of a hemiketal (II) has been isolated and shown to be the active intermediate in the production of the ketone.The stability of the salt and its potential reaction with the solvent dictates the type of reaction products.Low temperature favors stability of the lithium salt of the hemiketal whereby high yields of ketones are produced on hydrolysis.
- Chen, Loomis S.,Chen, Grace. J.,Tamborski, Christ
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p. 117 - 130
(2007/10/02)
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